EP0244565B1 - Method for charging tap water with ozone by means of a solid electrodes electrolytic cell - Google Patents

Method for charging tap water with ozone by means of a solid electrodes electrolytic cell Download PDF

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Publication number
EP0244565B1
EP0244565B1 EP19870101607 EP87101607A EP0244565B1 EP 0244565 B1 EP0244565 B1 EP 0244565B1 EP 19870101607 EP19870101607 EP 19870101607 EP 87101607 A EP87101607 A EP 87101607A EP 0244565 B1 EP0244565 B1 EP 0244565B1
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Prior art keywords
ozone
water
electrolytic cell
tap water
sidestream
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EP19870101607
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German (de)
French (fr)
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EP0244565A1 (en
Inventor
Hans Dr. Baumann
Hans-Jörg Christen
Hans-Peter Dr. Klein
Samuel Dr. Stucki
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BBC Brown Boveri AG Switzerland
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BBC Brown Boveri AG Switzerland
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/13—Ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/043—Treatment of partial or bypass streams

Definitions

  • the invention relates to a method for loading tap water with ozone according to the preamble of the claim.
  • the conventional methods generally require complex and costly devices, in particular as regards the mixing of the tap water with the ozone-containing air.
  • EP-A 0 068 522 describes a method and a device for ozonizing service water (drinking water, waste water, etc.) by using synthetic 0 3 production by means of electrolysis using an organic solid electrolyte. A partial flow of the medium to be treated can also be supplied. A comparatively concentrated Os solution is hereby injected into the main stream.
  • the invention has for its object to provide a method by means of which tap water can be doped with ozone in a simple and economical manner and without great expenditure on equipment.
  • the figure shows a flow diagram of the method and the schematic structure of a corresponding device.
  • 1 is the fresh water flow supplied to the device, which is divided into the main flow 2 and the secondary flow 3 at the inlet.
  • 4 is a two-part water softening system connected to two shut-off valves with 3, the individual chambers (4a, 4b) of which are operated alternately.
  • the intermittent supply of NaCI as regeneration salt is indicated by arrows.
  • 5 represents an electrolysis cell with solid electrolyte, which doped the desalted side stream 3 with ozone.
  • the two streams 2 and 3 are brought together again in the mixer 6 and mixed intimately.
  • a method according to the figure had the following operating parameters:
  • the positive electrode (anode) consisted of a 1 mm thick, Pb0 2- coated porous titanium plate, while a porous composite body made of graphite and polytetrafluoroethylene was used as the negative electrode (cathode).
  • the ratio 0 2 to 0 3 is on average as 85% by weight to 15% by weight.
  • the mixer 6 was designed as a static mixer.
  • the advantages of this method are that the water softening system 4 and the electrolysis cell 5 only for the amount of water in the side stream. 3 must be dimensioned and there is no poisoning of the electrolytic cell by divalent cations contained in the tap water (especially calcium).
  • the proportion of the secondary stream 3 is 0.5 to 3% by volume of the amount of the fresh water stream 1, its ozone concentration after the electrolytic cell 5 reaching 30-120 g per m 3 H 2 O.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Description

Die Erfindung geht aus von einem Verfahren zur Beladung von Leitungswasser mit Ozon nach der Gattung des Oberbegriffs des Patentanspruchs.The invention relates to a method for loading tap water with ozone according to the preamble of the claim.

Zur Entkeimung von Leitungswasser wird oft von dessen Beladung mit Ozon Gebrauch gemacht. Dabei können die herkömmlichen Verfahren in folgende Teilschritte unterteilt werden:

  • - Luft-Aufbereitung (Trocknung)
  • - Ozonherstellung durch stille elektrische Entladung
  • - Inberührungbringen des Leitungswassers mit dem ozonhaltigen Luftstrom (z.B. in einer Blasensäule)
  • - Beseitigung des Restozons
To disinfect tap water, it is often used to load it with ozone. The conventional processes can be divided into the following sub-steps:
  • - air treatment (drying)
  • - Production of ozone through silent electrical discharge
  • - bringing the tap water into contact with the air flow containing ozone (e.g. in a bubble column)
  • - Elimination of the residual ozone

Vergl. zum Beispiel C.M. Robson, «Design Engineering Aspects of Ozonation Systems», Handbook of Ozone Technology and Applications, R.G. Rice and A. Netzer, Eds., Vol. 1, Ann Arbor, 1982.Cf. for example C.M. Robson, “Design Engineering Aspects of Ozonation Systems”, Handbook of Ozone Technology and Applications, R.G. Rice and A. Netzer, Eds., Vol. 1, Ann Arbor, 1982.

Die herkömmlichen Verfahren bedingen in der Regel aufwendige und kostspielige Vorrichtungen, insbesondere was die Vermischung des Leitungswassers mit der ozonhaltigen Luft betrifft.The conventional methods generally require complex and costly devices, in particular as regards the mixing of the tap water with the ozone-containing air.

Es ist schon vorgeschlagen worden, Ozon auf elektrolytischem Wege unter Zuhilfenahme von sehr reinem Wasser herzustellen (Vergl. H.-P. Klein und S. Stucki, «The Production of Ozone by Elektrolysis and its Application in high purity Water Systems», Conference Proceedings 7th Ozone World Congress, 9-12 Sept. 1985, Tokyo; US-A 4 416 747).It has already been proposed to produce ozone electrolytically using very pure water (see H.-P. Klein and S. Stucki, "The Production of Ozone by Electrolysis and its Application in high purity Water Systems", Conference Proceedings 7th Ozone World Congress, 9-12 Sept. 1985, Tokyo; US-A 4 416 747).

In der EP-A 0 068 522 ist ein Verfahren sowie eine Vorrichtung zur Ozonisierung von Gebrauchswässern (Trinkwasser, Abwasser, etc.) durch Anwendung der synthetischen 03-Herstellung mittels Elektrolyse unter Verwendung eines organischen Feststoffelektrolyten beschrieben. Dabei kann auch ein Teilstrom des zu behandelnden Mediums zugeführt werden. Es wird hiermit eine vergleichsweise konzentrierte Os-Lösung in den Hauptstrom injiziert.EP-A 0 068 522 describes a method and a device for ozonizing service water (drinking water, waste water, etc.) by using synthetic 0 3 production by means of electrolysis using an organic solid electrolyte. A partial flow of the medium to be treated can also be supplied. A comparatively concentrated Os solution is hereby injected into the main stream.

Für die Dotierung von Leitungswasser mit Ozon sind die oben beschriebenen Verfahren weniger gut geeignet, da grosse Mengen gefördert werden müssen und sich ein beträchtlicher apparativer Aufwand ergibt. Bei direkter Verwendung des elektrolytischen Verfahrens würde die Zelle in verhältnismässig kurzer Zeit durch die im Leitungswasser vorhandenen zweiwertigen Kationen blockiert, so dass deren unmittelbare Verwendung unwirtschaftlich wäre.The methods described above are less suitable for doping tap water with ozone, since large quantities have to be pumped and there is considerable outlay on equipment. If the electrolytic method were used directly, the cell would be blocked in a relatively short time by the divalent cations present in the tap water, so that their direct use would be uneconomical.

Es besteht daher ein Bedürfnis nach Verbesserung und Vereinfachung der bekannten Methoden und Vorrichtungen.There is therefore a need to improve and simplify the known methods and devices.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren anzugeben, mit dessen Hilfe Leitungswasser auf einfache und wirtschaftliche Weise und ohne grossen apparativen Aufwand mit Ozon dotiert werden kann.The invention has for its object to provide a method by means of which tap water can be doped with ozone in a simple and economical manner and without great expenditure on equipment.

Diese Aufgabe wird durch die im kennzeichnenden Teil des Patentanspruchs angegebenen Merkmale gelöst.This object is achieved by the features specified in the characterizing part of the patent claim.

Die Erfindung wird anhand des nachfolgenden, durch eine Figur näher erläuterten Ausführungsbeispiels beschrieben.The invention is described with reference to the following exemplary embodiment, which is explained in more detail by a figure.

Dabei zeigt die Figur ein Fliessbild des Verfahrens bzw. den schematischen Aufbau einer entsprechenden Vorrichtung. 1 ist der der Vorrichtung zugeführte Frischwasserstrom, welcher im Eintritt in den Hauptstrom 2 und den Nebenstrom 3 aufgeteilt wird. 4 ist eine über zwei Absperrhahnen mit 3 verbundene zweiteilige Wasserenthärtungsanlage deren einzelne Kammern (4a, 4b) abwechslungsweise betrieben werden. Die intermittierende Zufuhr von NaCI als Regeneriersalz ist durch Pfeile angedeutet. 5 stellt eine Elektrolysezelle mit Feststoffelektrolyt dar, welche den entsalzten Nebenstrom 3 mit Ozon dotiert. Die beiden Ströme 2 und 3 werden im Mischer 6 wieder zusammengeführt und innig vermischt.The figure shows a flow diagram of the method and the schematic structure of a corresponding device. 1 is the fresh water flow supplied to the device, which is divided into the main flow 2 and the secondary flow 3 at the inlet. 4 is a two-part water softening system connected to two shut-off valves with 3, the individual chambers (4a, 4b) of which are operated alternately. The intermittent supply of NaCI as regeneration salt is indicated by arrows. 5 represents an electrolysis cell with solid electrolyte, which doped the desalted side stream 3 with ozone. The two streams 2 and 3 are brought together again in the mixer 6 and mixed intimately.

Ausführungsbeispiel:Design example:

Ein Verfahren gemäss Figur wies die nachfolgenden Betriebsparameter auf:

Figure imgb0001
A method according to the figure had the following operating parameters:
Figure imgb0001

Als Wasserenthärtungsanlage 4 wurden zwei Kationenaustauschersäulen benutzt, welche periodisch mit NaCI-Lösung regeneriert wurden. Dieser Tandembetrieb gestattete eine kontinuierliche Arbeitsweise. Von der Wasserenthärtungsanlage 4 wurde der Nebenstrom 3 in den Anodenraum einer Elektrolysezelle geleitet. Letztere war mit einem Feststoffelektrolyten in Form einer perfluorierten lonenaustauschermembran (Handelsname "Nafion" von Du Pont) ausgerüstet. Beidseits der Membran befanden sich poröse Elektroden, welche mit einer Flächenpressung von 400 N/cm2 gegeneinander gedrückt wurden. Die positive Elektrode (Anode) bestand aus einer 1 mm dicken, mit Pb02 überzogenen porösen Titanplatte, während als negative Elektrode (Kathode) ein poröser Verbundkörper aus Graphit und Polytetrafluoräthylen diente. Zwischen der Kathode und dem Feststoffelektrolyt war eine dünne, als Elektrokatalysator wirkende Platinschicht angeordnet.Two cation exchange columns were used as water softening system 4, which were periodically regenerated with NaCl solution. This tandem operation allowed continuous operation. The secondary stream 3 was passed from the water softening system 4 into the anode compartment of an electrolysis cell. The latter was equipped with a solid electrolyte in the form of a perfluorinated ion exchange membrane (trade name "Nafion" from Du Pont). On both sides of the membrane were porous electrodes, which were pressed against each other with a surface pressure of 400 N / cm 2 . The positive electrode (anode) consisted of a 1 mm thick, Pb0 2- coated porous titanium plate, while a porous composite body made of graphite and polytetrafluoroethylene was used as the negative electrode (cathode). A thin platinum layer, acting as an electrocatalyst, was arranged between the cathode and the solid electrolyte.

Fliesst ein Gleichstrom durch die Elektrolysezelle, so wird an der Anode eine Mischung aus Sauerstoff und Ozon entwickelt. Das Verhältnis 02 zu 03 beträgt im Durchschnitt wie 85 Gew.-% zu 15 Gew.- %.If a direct current flows through the electrolytic cell, a mixture of oxygen and ozone is developed at the anode. The ratio 0 2 to 0 3 is on average as 85% by weight to 15% by weight.

Unmittelbar hinter der Elektrolysezelle 5 war eine Sonde zur Messung der im Wasser des Nebenstroms 3 gelösten prozentualen Ozonmenge angebracht. Im Mischer 6 wurde der ozonhaltige Nebenstrom 3 mit dem Hauptstrom 2 vereinigt. Der Mischer 6 war als statischer Mischer ausgeführt.Immediately behind the electrolysis cell 5 was a probe for measuring the percentage of ozone dissolved in the water of the bypass flow 3. The ozone-containing secondary stream 3 was combined with the main stream 2 in the mixer 6. The mixer 6 was designed as a static mixer.

Die Vorteile dieses Verfahrens bestehen darin, dass die Wasserenthärtungsanlage 4 und die Elektrolysezelle 5 nur für die Wassermenge des Nebenstroms. 3 dimensioniert werden müssen und eine Vergiftung der Elektrolysezelle durch zweiwertige, im Leitungswasser enthaltene Kationen (vor allem Kalzium) unterbleibt. Der Mengenanteil des Nebenstromes 3 beträgt 0,5 bis 3 Vol.-% der Menge des Frischwasserstroms 1, wobei seine Ozonkonzentration nach der Elektrolysezelle 5 30-120 g pro m3 H20 erreicht.The advantages of this method are that the water softening system 4 and the electrolysis cell 5 only for the amount of water in the side stream. 3 must be dimensioned and there is no poisoning of the electrolytic cell by divalent cations contained in the tap water (especially calcium). The proportion of the secondary stream 3 is 0.5 to 3% by volume of the amount of the fresh water stream 1, its ozone concentration after the electrolytic cell 5 reaching 30-120 g per m 3 H 2 O.

Claims (1)

  1. Process for ozonizing tap water by the water electrolysis method using a solid electrolyte, characterized in that the freshwater stream (1) is divided into a mainstream (2) and a sidestream (3), in that the water of the sidestream (3) is softened in a water-softening unit (4) and is fed to an electrolytic cell (5) and ozonized, and in that the resulting doped sidestream is combined with the mainstream (2) in a mixer (6), the sidestream (3) amounting to 0.5 to 3% by volume of the rate of the freshwater stream (1) and its ozone concentration downstream of the electrolytic cell (5) being 30 - 120 g per m3 of H20.
EP19870101607 1986-03-11 1987-02-06 Method for charging tap water with ozone by means of a solid electrodes electrolytic cell Expired - Lifetime EP0244565B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH995/86 1986-03-11
CH99586A CH667867A5 (en) 1986-03-11 1986-03-11 METHOD AND DEVICE FOR LOADING TAP WATER WITH OZONE USING AN OZONE GENERATING ELECTROLYSIS CELL EQUIPPED WITH A SOLID ELECTROLYTE.

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EP0244565A1 EP0244565A1 (en) 1987-11-11
EP0244565B1 true EP0244565B1 (en) 1990-05-30

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JP (1) JPS62221490A (en)
CA (1) CA1315236C (en)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0813356B2 (en) * 1988-09-29 1996-02-14 ペルメレック電極株式会社 Water treatment method and apparatus using electrolytic ozone
JPH0326389A (en) * 1989-06-22 1991-02-04 O D S:Kk Active-oxygen reactor
JP3007137B2 (en) * 1990-11-27 2000-02-07 ペルメレック電極株式会社 Electrolytic ozone generation method and apparatus
FR2698349B1 (en) * 1992-11-24 1995-06-09 Trailigaz INSTALLATION FOR THE REMOVAL OF MICRO-POLLUTANTS FROM RAW WATER, PARTICULARLY DRILLING WATER, BY COMBINED ACTION OF OZONE AND HYDROGEN PEROXIDE.
CN1101785C (en) * 1996-03-28 2003-02-19 费罗马托姆Anp有限责任公司 Gasification device
US6171551B1 (en) * 1998-02-06 2001-01-09 Steris Corporation Electrolytic synthesis of peracetic acid and other oxidants
ATE245351T1 (en) 1999-08-05 2003-08-15 Steris Inc ELETROLYTIC SYNTHESIS OF PERACETIC ACID
JP2002263650A (en) * 2001-03-14 2002-09-17 Sanyo Electric Co Ltd Method for generating ozone by electrolysis and ozone generating device
US20080251373A1 (en) * 2004-10-21 2008-10-16 Ecozone Pty. Ltd. Potable Water Purifier For Pressurised Systems For Buildings

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Publication number Priority date Publication date Assignee Title
US4316787A (en) * 1979-08-06 1982-02-23 Themy Constantinos D High voltage electrolytic cell
EP0068522B1 (en) * 1981-05-11 1984-10-24 BBC Aktiengesellschaft Brown, Boveri & Cie. Process and apparatus for the synthetic preparation of ozone by electrolysis, and its application

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JPS62221490A (en) 1987-09-29
DE3762961D1 (en) 1990-07-05
CA1315236C (en) 1993-03-30
EP0244565A1 (en) 1987-11-11

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